Alkyd resins modified with parahydroxyphenylacetic acid



United State 2. 8 6 .v ALKYD RESINSMODIFIED wrrn PARA- HYDROXYPHENYLACETIC Aci in Raymond L. Heinrich, Baytown, Tex.,, and David A. Q

Berry, Columbus, and Robert L. Christian, Gahanna, Ohio, assignors, by mesne assignments, to Esso Research and Engineering Company, Elizabeth,N.J., 21.

corporation of Delaware No Drawing. FiledOct. 2, 1959, Ser. No.1 843,918

3 Claims. cram-.22

This invention relates to modified alkyd resins. More .Paie t A i H Preferred polyhydric alcohols to be used in the preparation of the alkyds are the aliphatic alcohols possessing from 3 to 6 hy droxyl groups and containing from 13 to particularly, this invention relates to modified alkyd resins ofimproved hardness and drying characteristics.

'Alkyd resins are widely used in thepreparation of surface coating compositions. A particularly desired classfj of alkyd I'CSlHS are the sorcalled foil-modified alkyd resins employed in coatings and prepared by the intercondensat'ion of a polybasic acid (preferably dibasic), a

polyol, and an unsaturated fatty acid derived from a glyceride oil.

The present invention is directed to a discovery in the field of oil-modified alkyd resins which not only permits the inclusion of parmhydroxyphenyl-acetic acid as a raw material but which also provides oil-modified alkyd resins of improved physical and chemical properties.

It has now been discovered that alkyd resins composi tions of improved physical properties may be obtained by replacing from about to about 75 mol percent (preferably to mol percent) of the fatty acid component of the alkyd resin with para-hydroxyphenylacetic acid. In particular, the alkyd resin coating compositions of the present invention are characterized by satisfactory drying times and the films prepared therefrom are characterized by excellent flexibility and hardness.

14 carbon atoms, such as glycerol pentaerythritol, manitol, 1,4,6-octanetriol, and 1,3,5-hexanetriol.

The polyhydric alcohol (polyol) should contain an average of from about 2.5 to about 4.5 hydroxyl groups per molecule and, preferably, about 3 hydroxyl groups per molecule. if i A wide variety ofjunsaturated fatty acids may be utilized in the preparation of modified alkyd resins, the

source of the fatty acid normally being a naturally occurring vegetable or marine oil. Thus, there may be used Alkyd resin chemistry is well known to those skilled in the art and, in the interest of brevity, will not be discussed in detail. The preparation and physical properties of alkydresins are described in numerous texts, such as the polyethylenic acid's derived from the drying oils, and their derivatives, such as their esters, and the like. Examples ofthese acids and derivatives include the acids derived from oil; such as linseed, soyalbean, perilla, oitica, tung, walnut, and dehydrated castor oil, linoleic, linolenic, 9,12-octadecadienoic, 9,l2,l5'octadecatrienoic, and eleostearic acid; the monohydric alcohol esters of the drying oil acids, such as methyl eleostearate, butyl eleostearate, ethyl 9-l2-octadecadienoate, butyl 9,12,lS-octadecatrienoate, and octyl 9,12-octadecadienoate; the glycerides of the fatty acids Oflhfi drying oils, 1 such as the m onoglyceride of the linseed oil acids, the" diglyceride of the soyabean acids, the monoglyceride of the tung oil acids, and the drying oils themselves, such as 1..ng oil, soyabean oil. hempseed, sardine, and the like. The preferred modifiers comprise the drying oil fatty acids ,and th'eir monoand diglycerides. Particularly preferred modifiers are the drying oil fatty acids containing at least 12 carbon atoms.

vol. I to Organic Coating Technology, Henry Fleming Payne, John Wiley and Sons, Inc., N.Y., 1954.

The polycarboxylic acids used in the preparation of the novel alkydsmay be any of those generally employed in the preparation of this type of resin. These acids may possess two, three, four, or more carboxyl groups and may be aliphatic, alicyclic, heterocyclic, or aromatic and i may be saturated or uns turated. Examples of such acids are malonic, glutaric, succinic, suberic, citric, tricarballylic,,cyclohexandicarboxylic, maleic, fumaric, itaconic,

citraconic, mesaconic, phthalic, isophthalic, terephthalic,

1,8-naphthalic, adipic, sebacic, azeleic, pimelic, chloro-- succinic, bromomaleic, and dichlorophthalic. p

The preferred polycarboxylic acids to be used in producing the novel alkyds are .the dicarboxylic acids containing from 2 to 10 carbon atoms, such as succinic,

adipic, maleic, phthalic, isophthalic and the like. Particularly preferred polycarboxylic acids are the aromatic dicarboxylic acids, containing from 6 to 10 carbon atoms wherein the two carboxyl groups are attached directly to the aromatic nucleus. H

In some cases it may be desirable to utilize other forms of the acids, such as the acid anhydrides or acid chlorides, as phthalic anhydride, maleic anhydride, isophthaloyl chloride, and the like.

The esters of the polybasic acids may be utilized in case the alkyds are to be produced by an ester exchange reaction. Preferred derivatives to be used for this purpose comprise the esters of the above-described acids and the lower saturated rnonohydricalcohols, preferably those 1 If desired, other modifiers in addition to those described above maybe utilized in the preparation of the novel alkyds. Such modifiers include the protein plastics, natural resins such asrosin, synthetic resins as the nitrocellulose,phenol-formaldehyde, urea-formaldehyde and melamine type resins, synthetic resins obtained by the additional polymerization of unsaturated compounds, such as styrene, alpha-methylstyrene, vinyl chloride, vinylidene chloride, vinyl acetate, methyl acrylate, methyl methacrylate, and the like, as well as mixtures thereof.

In general, the polybasic acid, polyol, and fatty acid are interreacted in proportions sufficient to provide about a 5 to 25 weight percent excess of polyol. .Excess polyol may be defined as that amount of polyol in excess of the amount necessary to l,combine with the sum ofthe acid groups inthe fatty acid and the polybasic acid on a theoreticalbasis. Alkyd resins are conventionally characterized as short oil alkyd resins, medium. oil alkyd 1 resins, and long oil alkyd resins, depending upon the ratio of fatty acid ,to the dibasic acid in the preparation of the resin. Long oil alkydresins are normally prepared by the interreaction of about 3.1 to about 3.4 mol equivalents of polyol, with about 2 mol equivalents, of, polycarboxylic acid and 1 mol, equivalent of unsaturated fatty acid. Progressively larger amounts of polycarboxylic acid and progressively smaller amounts of unsaturated fatty acid are utilized to provide for a shorter oil length. Thus, short oil alkyd resins may be prepared by the intercondensation ofabout 3.1 to about 3.4 mol equivalents of polyol with about, 2.3j to ,about.,2.5 H1011];

equivalents of polycarboxylic acid and from about 0.7 to about 0.5 mol equivalent of unsaturated fatty acid.

Accordingly, the alkyd resin compositions of the present invention may be defined as intercondensation products of about 3.1 to about 3.4 moi equivalents of a polyol containing about 2.5. to 4.5 hydroxyl groups per molecule with about 2 to 2.5 mol equivalents of a poiycarboxyiic acid and about 1 to about 0.5 mol equivalent of a modifier consisting of about 45 to 75 mol percent, preferably 55 to 65 mol percent, of an unsaturated fatty acid and, correspondingly, from about 55 to 25 mo] percent, preferably 45 to 35 mol percent, of para-hydroxyphenylacetic acid was replaced with the acid modifier on a mol percent basis, and the weight percent of acid modifier utilized, based upon the total charge. In addition, the drying time of the alkyd resins prepared in the above-described fashion is given, together with the hardness of films prepared by drying of the alkyd resin compositions. The drier concentration employed for the air drying tests was about 0.5 weight percent of lead naphthenate and about 0.05 weight percent of cobalt naphthenate, based on the weight of the resin solids. For the baked film tests, cobalt naphthenate was employed in an amount of 0.02 weight percent.

T able I.Cmp0siri0n and physical characteristics of modified glycerine-soya-phzhalic-alkyd resins Modifier None Phcnylacetic Acid P-HydroxyAPihdenyi Acetic Mole equivalent replacement 0 40 50 60 40 50 60 Weight percent 0 13. 0 16. 7 20. 6 14. 2 18. 4 22. 8 Fatty acid, percent. 41. 8 35. 8 29. 7 39. 6 34 28. 2 Final acid nnmber 4 7 7.1 6.4 4.0 Color. 60 percent in mi 9. 9. 5 10.0 8 6 6 Znpon tack-free time hours 100 45-50 4&50 45- 50 2 0,33 Swarri hardness:

Bake:

48 hours 10 12 12 6 l 12 24 12 14 8 Fair Fair Fair Fair Good Good Poor Poor Poor Poor Good Good Passed Passed Pa sed Passed Passed Passed Passed Passed Passed Passed Passed Passed l 12 hours.

acid. Thus, improved short oil, medium oil and long oil alkyd resins are provided in accordance with the present invention. The improvement is most pronounced with long'oil alkyd resins.

The invention will be further illustrated by the following specific example which is given by way of illustration and not as limitations on the scope of this invention.

EXAMPLE I A plurality of alkyd resins were prepared utilizing phthalic anhydride, glycerol, soya fatty acids and, except for the base resin, an aromatic monocarboxylic acid. The amount of fatty acid utilized in preparing each of the resins was determined by the extent to which the fatty acid was to be replaced, on a molar basis, by the aromatic monocarboxylic acid. About a 6 to 7 percent molar excess of glycerol was used in order to obtain equivalent degrees of polymerization.

All of the ingredients were charged at once to a flask fitted with a reflux condenser connected to a Dean Stark tube. The charge was heated to a temperature of about 450 F. over a 3 to 4 hour period and maintained at this temperature for about 5 to 3'hours. An atmosphere of refluxing Xylene vapor was maintained over the cook and vigorous agitation was employed. Water was azeotropically removed as evolved during the course of y the reaction. I

At the end of the reaction, the alkyd resin was diluted while hot'with solvent 'xylenes to provide alkyd resin formulations containing about 60 weight percent of resin solids. 0.001 inch and baked films of about 0.0005 inch thickness were formed from the resin. The air-dried films were prepared and cured at 75 F. and 50 percent relative humidity; the baked filrns were cured at 250 F. for 30minutes. The films were tested for their physical properties.

In Table I there is listed the aromatic monocarboxylic acid modifiers employed, the extent to which the fatty Air-dried films having a thickness of about i From Table I it will be seen that unsatisfactory results were obtained when the alkyd resin was modified with phenylacetic acid. Thus, in the case of phenylacetic acid. excessively long dry times were required and, moreover, the physical properties of the resulting films were not satisfactory both with reference to hardness and also with reference to chemical resistance. When parahydroxyphenylacetic acid was utilized on a 40 percent replacement basis, the improvement was marginal. Improved results were obtained at 50 percent replacement. Note that the dry time was only two hours and that the resulting films were characterized by excellent hardness characteristics and also by good chemical resistance and equivalents of a polyol containing an average of from about 2.5 to 4.5 hydroxyl groups per molecule with from about 2 to 2.5 mol equivalents of a polycarboxyiic acid and, correspondingly, from about 1 to about 0.5 mol equivalent of a modifier component consisting of about 35 to 45 mol percent of an unsaturated fatty acid and, correspondingly, about 65 to 55.mol percent of. parahydroxyphenylacetic acid.

2. An alkyd resin coating composition as in claim wherein the polyol is glycerol and the dicarboxylic acid is phthalic anhydride. 1 1

3. An alkyd resin coating composition as in claim 1 wherein the polyol is glycerol, the dicarboxylic acid is phthalic anhydride, and the fatty acid is soya fatty acids.

Gray Apr. 24, 1945 

1. AN ALKYD RESIN COMPOSITION COMPRISING THE INTERCONDENSATION PRODUCT OF ABOUT 3.1 ABOUT 3.4 MOL EQUIVALENTS OF A POLYOL CONTAINING AN AVERAGE OF FROM ABOUT 2.5 TO 4.5 HYDROXYL GROUPS PER MOLECULE WITH FROM ABOUT 2 TO 2.5 MOL EQUIVALENTS OF A POLYCARBOXYLIC ACID AND, CORRESPONDINGLY, FROM ABOUT 1 TO ABOUT 0.5 MOL EQUIVALENT OF A MODIFIER COMPONENT CONSISTING OF ABOUT 35 TO 45 MOL PERCENT OF AN UNSATURATED FATTY ACID AND, CORRESPONDINGLY, ABOUT 65 TO 55 MOL PERCENT OF PARAHYDROXYPHENYLACETIC ACID. 